Abstract
The synthesis of a cyclohexane skeleton possessing different oxygenated functional groups at C–3, C–8 and C–9, and a Δ1,6-double bond has been accomplished in 10 steps with an overall 17% yield. This compound is a key intermediate for access to a wide range of compounds of the bioactive trisporoid family. The synthetic sequence consists of the preparation of a properly functionalized epoxygeraniol derivative, and its subsequent stereoselective cyclization mediated by Ti(III). This last step implies a domino process that starts with a homolytic epoxide opening followed by a radical cyclization and regioselective elimination. This concerted process gives access to the cyclohexane moiety with stereochemical control of five of its six carbon atoms.
Highlights
Trisporic acids (Figure 1), their precursors and derivatives are an interesting group of bioactive natural products biosynthetically derived from the degradative oxidation of -carotene
These facts are well reported for different species of fungi such as Blakeslea trispora (Choaneforaceae family) [1,2,3], Phycomyces blakesleeanus (Phycomycetaceae family) [4], Mucor mucedo (Mocuraceae family) [2,5,6,7], and the homothallic Zygorhynchus moelleri (Mocuraceae family) [8]
It has been demonstrated that the recognition between the parasite fungi Parasitella parasitica (Mocuraceae family) and the host Absidia glauca is mediated by trisporoids which are responsible for sexual phenomena [10,11]
Summary
Trisporic acids (Figure 1), their precursors and derivatives are an interesting group of bioactive natural products biosynthetically derived from the degradative oxidation of -carotene. Ti(III)-mediated synthesis of apotrisporoids and trisporoids based on bioinspired cyclizations Following this strategy, a significant advance in the development of a selective synthesis of highly functionalized key intermediates such as II (Schemes 1 and 2) is described. A significant advance in the development of a selective synthesis of highly functionalized key intermediates such as II (Schemes 1 and 2) is described These may be considered as effective precursors for the synthesis of trisporic acids and their corresponding alcohol derivatives (trisporols), mainly for their use as a standard either in subsequent identifications, quantifications, and biological activity tests (as fungi pheromones). Having in consideration the objective to achieve straightforward functional modifications at C–2, C–4, C–5, C–13 and C–17 (Figure 1), such approach would open the door to the synthesis of the majority of the known natural trisporoids C18; to early trisporoids such as trisporins and to late ones such as trisporols, trisporic acid and methyl trisporates
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